1932

Abstract

The nonadiabatic coupling of electronic and vibrational degrees of freedom is the defining feature of electronically excited states of polyatomic molecules. Once considered a theoretical curiosity, conical intersections (CIs) are now generally accepted as being the dominant source of coupled charge and vibrational energy flow in molecular excited states. Passage through CIs leads to the conversion of electronic to vibrational energy, which drives the ensuing photochemistry, isomerization being a canonical example. It has often been remarked that the CI may be thought of as a transition state in the excited state. As such, we expect that both the direction and the velocity of approach to the CI will matter. We explore this suggestion by looking for dynamical aspects of passage through CIs and for analogies with well-known concepts from ground-state reaction dynamics. Great progress has been made in the development of both experimental techniques and ab initio dynamics simulations, to a degree that direct comparisons may now be made. Here we compare time-resolved photoelectron spectroscopy results with on-the-fly ab initio multiple spawning calculations of the experimental observables, thereby validating each. We adopt a phenomenological approach and specifically concentrate on the excited-state dynamics of the C=C bond in unsaturated hydrocarbons. In particular, we make use of selective chemical substitution (such as replacing an H atom by a methyl group) so as to alter the inertia of certain vibrations relative to others, thus systematically varying (mass-weighted) directions and velocities of approach to a CI. Chemical substituents, however, may affect both the nuclear and electronic components of the total wave function. The former, which we call an inertial effect, influences the direction and velocity of approach. The latter, which we call a potential effect, modifies the electronic structure and therefore the energetic location and topography of the potential energy surfaces involved. Using a series of examples, we discuss both types of effects. We argue that there is a need for dynamical pictures and simple models of nonadiabatic dynamics at CIs and hope that the phenomenology presented here will help inspire such developments.

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2018-04-20
2024-04-15
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Literature Cited

  1. Michl J, Bonačić-Koutecký V. 1.  1990. Electronic Aspects of Organic Photochemistry New York: Wiley
  2. Yarkony DR. 2.  2004. Conical intersections: their description and consequences. Conical Intersections: Electronic Structure, Dynamics and Spectroscopy W Domcke, DR Yarkony, H Köppel 41–128 Singapore: World Sci. [Google Scholar]
  3. Worth GA, Cederbaum LS. 3.  2004. Beyond Born–Oppenheimer: molecular dynamics through a conical intersection. Annu. Rev. Phys. Chem. 55:127–58 [Google Scholar]
  4. Levine B, Martínez T. 4.  2007. Isomerization through conical intersections. Annu. Rev. Phys. Chem. 58:613–34 [Google Scholar]
  5. Matsika S, Krause P. 5.  2011. Nonadiabatic events and conical intersections. Annu. Rev. Phys. Chem. 62:621–43 [Google Scholar]
  6. Richter M, Marquetand P, González-Vázquez J, Sola I, González L. 6.  2011. SHARC: ab inito molecular dynamics with surface hopping in the adiabatic representation including arbitrary couplings. J. Chem. Theor. Comput. 7:1253–58 [Google Scholar]
  7. Ashfold M, Devine A, Dixon R, King G, Nix M, Oliver T. 7.  2008. Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol. PNAS 105:12701–6 [Google Scholar]
  8. Marchetti B, Karsili T, Ashfold M, Domcke W. 8.  2016. A ‘bottom up’, ab initio computational approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs. Phys. Chem. Chem. Phys. 18:20007–27 [Google Scholar]
  9. Ashfold M, Bain M, Hansen C, Ingle R, Karsili T. 9.  et al. 2017. Exploring the dynamics of the photoinduced ring-opening of heterocyclic molecules. J. Phys. Chem. Lett. 8:3440–51 [Google Scholar]
  10. Klessinger M. 10.  1995. Conical intersections and the mechanism of singlet photoreactions. Angew. Chem. Int. Ed. 34:549–51 [Google Scholar]
  11. Bernardi F, Olivucci M, Robb MA. 11.  1996. Potential energy surface crossings in organic photochemistry. Chem. Soc. Rev. 25:321–28 [Google Scholar]
  12. Pechukas P. 12.  1981. Transition-state theory. Annu. Rev. Phys. Chem. 32:159–77 [Google Scholar]
  13. Truhlar D, Garrett B, Klippenstein S. 13.  1996. Current status of transition state theory. J. Phys. Chem. 100:12771–800 [Google Scholar]
  14. Miller W. 14.  1998. Spiers memorial lecture: Quantum and semiclassical theory of chemical reaction rates. Faraday Discuss 110:1–21 [Google Scholar]
  15. Guo H, Jiang B. 15.  2014. The sudden vector projection model for reactivity: mode specificity and bond selectivity made simple. Acc. Chem. Res. 47:3679–85 [Google Scholar]
  16. Ma X, Hase W. 16.  2017. Perspective: Chemical dynamics simulations of non-statistical reaction dynamics. Phil. Trans. R. Soc. A 375:20160204 [Google Scholar]
  17. Schalk O, Boguslavskiy A, Stolow A, Schuurman M. 17.  2011. Through-bond interactions and the localization of excited state dynamics. J. Am. Chem. Soc. 133:16451–58 [Google Scholar]
  18. Malhado J, Hynes J. 18.  2016. Non-adiabatic transition probability dependence on conical intersection topography. J. Chem. Phys. 145:194104 [Google Scholar]
  19. Stolow A. 19.  2003. Femtosecond time-resolved photoelectron spectroscopy of polyatomic molecules. Annu. Rev. Phys. Chem. 54:89–119 [Google Scholar]
  20. Stolow A, Bragg A, Neumark D. 20.  2004. Femtosecond time-resolved photoelectron spectroscopy. Chem. Rev. 104:1719–57 [Google Scholar]
  21. Suzuki T. 21.  2006. Femtosecond time-resolved photoelectron imaging. Annu. Rev. Phys. Chem. 57:555–92 [Google Scholar]
  22. Stolow A, Underwood J. 22.  2008. Time-resolved photoelectron spectroscopy of nonadiabatic dynamics in polyatomic molecules. Adv. Chem. Phys. 139:497–583 [Google Scholar]
  23. Stock G, Domcke W. 23.  1997. Theory of ultrafast nonadiabatic excited-state processes and their spectroscopic detection in real time. Adv. Chem. Phys. 100:1–169 [Google Scholar]
  24. Seideman T. 24.  2002. Time-resolved photoelectron angular distributions: concepts, applications, and directions. Annu. Rev. Phys. Chem. 53:41–65 [Google Scholar]
  25. Reid KL. 25.  2003. Photoelectron angular distributions. Annu. Rev. Phys. Chem. 54:397–424 [Google Scholar]
  26. Wang K, McKoy V, Hockett P, Schuurman MS. 26.  2014. Time-resolved photoelectron spectra of CS2: dynamics at conical intersections. Phys. Rev. Lett. 112:113007 [Google Scholar]
  27. Martínez TJ, Ben-Nun M, Levine RD. 27.  1996. Multi-electronic-state molecular dynamics: a wave function approach with applications. J. Phys. Chem. 100:7884–95 [Google Scholar]
  28. Martínez TJ, Ben-Nun M, Levine RD. 28.  1997. Molecular collision dynamics on several electronic states. J. Phys. Chem. A 101:6389–402 [Google Scholar]
  29. Ben-Nun M, Quenneville J, Martínez TJ. 29.  2000. Ab initio multiple spawning: photochemistry from first principles quantum molecular dynamics. J. Phys. Chem. A 104:5161–75 [Google Scholar]
  30. Ben-Nun M, Martínez TJ. 30.  1998. Nonadiabatic molecular dynamics: validation of the multiple spawning method for a multidimensional problem. J. Chem. Phys. 108:7244–57 [Google Scholar]
  31. Ben-Nun M, Martínez TJ. 31.  2002. Ab initio quantum molecular dynamics. Adv. Chem. Phys. 121:439–512 [Google Scholar]
  32. Virshup AM, Punwong C, Pogorelov TV, Lindquist BA, Ko C, Martínez TJ. 32.  2009. Photodynamics in complex environments: ab initio multiple spawning quantum mechanical/molecular mechanical dynamics. J. Phys. Chem. B 113:3280–91 [Google Scholar]
  33. Tully JC, Preston RK. 33.  1971. Trajectory surface hopping approach to nonadiabatic molecular collisions: the reaction of H+ with D2. J. Chem. Phys. 55:562–72 [Google Scholar]
  34. Tully JC. 34.  1990. Molecular dynamics with electronic transitions. J. Chem. Phys. 93:1061–71 [Google Scholar]
  35. Worth GA, Burghardt I. 35.  2003. Full quantum mechanical molecular dynamics using Gaussian wavepackets. Chem. Phys. Lett. 368:502–8 [Google Scholar]
  36. Richings G, Polyak I, Spinlove K, Worth G, Burghardt I, Lasorne B. 36.  2015. Quantum dynamics simulations using Gaussian wavepackets: the vMCG method. Int. Rev. Phys. Chem. 34:269–308 [Google Scholar]
  37. Saita K, Shalashilin DV. 37.  2012. On-the-fly ab initio molecular dynamics with multiconfigurational Ehrenfest method. J. Chem. Phys. 137:22A506 [Google Scholar]
  38. Atchity Y, Xantheas X, Rudenberg K. 38.  1991. Potential energy surfaces near intersections. J. Chem. Phys. 95:1862–76 [Google Scholar]
  39. Yarkony DR. 39.  2001. Nuclear dynamics near conical intersections in the adiabatic representation: I. The effects of local topography on interstate transitions. J. Chem. Phys. 114:2601–13 [Google Scholar]
  40. Ben-Nun M, Molnar F, Schulten K, Martínez TJ. 40.  2002. The role of intersection topography in bond selectivity of cis-trans photoisomerization. PNAS 99:1769–73 [Google Scholar]
  41. Silicia F, Blancafort L, Bearpark M, Robb M. 41.  2007. Quadratic description of conical intersections: characterization of critical points on the extended seam. J. Phys. Chem. A. 11:2182–92 [Google Scholar]
  42. Krause P, Matsika S, Kotur M, Weinacht T. 42.  2002. The influence of excited state topology on wavepacket delocalization in the relaxation of photoexcited polyatomic molecules. J. Chem. Phys. 137:22A537 [Google Scholar]
  43. Yarkony DR. 43.  2005. Statistical and nonstatistical nonadiabatic photodissociation from the first excited state of the hydroxymethyl radical. J. Chem. Phys. 122:084316 [Google Scholar]
  44. Freed KF. 44.  1976. Energy dependence of electronic relaxation processes in polyatomic molecules. Radiationless Processes in Molecules and Condensed Phases FK Fong 23–168 Berlin: Springer [Google Scholar]
  45. Avouris P, Gelbart WM, El-Sayed MA. 45.  1977. Nonradiative electronic relaxation under collision-free conditions. Chem. Rev. 77:793–833 [Google Scholar]
  46. Penner AP, Siebrand W, Zgierski MZ. 46.  1978. Radiationless decay of vibronically coupled electronic states. J. Chem. Phys. 69:5496–508 [Google Scholar]
  47. Köppel H, Domcke W, Cederbaum LS. 47.  1984. Multimode molecular dynamics beyond the Born–Oppenheimer approximation. Adv. Chem. Phys. 57:59–246 [Google Scholar]
  48. Köppel H, Domcke W, Cederbaum LS. 48.  2004. The multi-mode vibronic-coupling approach. Conical Intersections: Electronic Structure, Dynamics and Spectroscopy W Domcke, DR Yarkony, H Köppel 323–68 Singapore: World Sci. [Google Scholar]
  49. Hazra A, Nooijen M. 49.  2005. Comparison of various Franck–Condon and vibronic coupling approaches for simulating electronic spectra: the case of the lowest photoelectron band of ethylene. Phys. Chem. Chem. Phys. 7:1759–71 [Google Scholar]
  50. Klein K, Garand E, Ichino T, Neumark DM, Gauss J, Stanton JF. 50.  2011. Quantitative vibronic coupling calculations: the formyloxyl radical. Theor. Chem. Acc. 129:527–43 [Google Scholar]
  51. Dillon J, Yarkony DR, Schuurman MS. 51.  2011. On the construction of quasidiabatic state representations of bound adiabatic state potential energy surfaces coupled by accidental conical intersections: incorporation of higher order terms. J. Chem. Phys. 134:044101 [Google Scholar]
  52. Rabidoux SM, Eijkhout V, Stanton JF. 52.  2014. Parallelization strategy for large-scale vibronic coupling calculations. J. Phys. Chem. A 118:12059–68 [Google Scholar]
  53. Fuß W. 53.  2013. Where does the energy go in fs-relaxation?. Chem. Phys. 425:96–103 [Google Scholar]
  54. Fuß W. 54.  2015. Predistortion amplified in the excited state. J. Photochem. Photobiol. A 297:45–57 [Google Scholar]
  55. Barbatti M, Paier J, Lischka H. 55.  2004. Photochemistry of ethylene: a multireference configuration interaction investigation of the excited-state energy surfaces. J. Chem. Phys. 121:11614–24 [Google Scholar]
  56. Tao H, Allison TK, Wright TW, Stooke AM, Khurmi C. 56.  et al. 2011. Ultrafast internal conversion in ethylene. I. The excited state lifetime. J. Chem. Phys. 134:244306 [Google Scholar]
  57. Allison TK, Tao H, Glover WJ, Wright TW, Stooke AM. 57.  et al. 2012. Ultrafast internal conversion in ethylene. II. Mechanisms and pathways for quenching and hydrogen elimination. J. Chem. Phys. 136:124317 [Google Scholar]
  58. Mori T, Glover WJ, Schuurman MS, Martínez TJ. 58.  2012. Role of Rydberg states in the photochemical dynamics of ethylene. J. Phys. Chem. A 116:2808–18 [Google Scholar]
  59. Kobayashi T, Horio T, Suzuki T. 59.  2015. Ultrafast deactivation of the ππ*(V) state of ethylene studied using sub-20 fs time-resolved photoelectron imaging. J. Phys. Chem. A 119:9518–23 [Google Scholar]
  60. Champenois EG, Shivaram NH, Wright TW, Yang CS, Belkacem A, Cryan JP. 60.  2016. Involvement of a low-lying Rydberg state in the ultrafast relaxation dynamics of ethylene. J. Chem. Phys. 144:014303 [Google Scholar]
  61. Ben-Nun M, Martínez TJ. 61.  2000. Photodynamics of ethylene: ab initio studies of conical intersections. Chem. Phys. 259:237–48 [Google Scholar]
  62. Quenneville J, Ben-Nun M, Martínez TJ. 62.  2001. Photochemistry from first principles advances and future prospects. J. Photochem. Photobiol. A: Chem. 144:229–35 [Google Scholar]
  63. Barbatti M, Ruckenbauer M, Lischka H. 63.  2005. The photodynamics of ethylene: a surface-hopping study on structural aspects. J. Chem. Phys. 122:174307 [Google Scholar]
  64. Tao H, Levine BG, Martínez TJ. 64.  2009. Ab initio multiple spawning dynamics using multi-state second-order perturbation theory. J. Phys. Chem. A 113:13656–62 [Google Scholar]
  65. Brooks BR, Schaefer HF. 65.  1979. Sudden polarization: pyramidalization of twisted ethylene. J. Am. Chem. Soc. 101:307–11 [Google Scholar]
  66. Bonačić-Koutecký V, Bruckmann P, Hiberty P, Koutecký J, Leforestier C, Salem L. 66.  1975. Sudden polarization in the zwitterionic Z1 excited states of organic intermediates. Photochemical implications. Angew. Chem. Int. Ed. 14:575–76 [Google Scholar]
  67. Wu G, Boguslavskiy AE, Schalk O, Schuurman M, Stolow A. 67.  2011. Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: the π3s Rydberg state. J. Chem. Phys. 135:164309 [Google Scholar]
  68. Lee A, Coe J, Ho M, Lee S, Cheng B. 68.  et al. 2007. Substituent effects on dynamics at conical intersections: α-enones. J. Phys. Chem. 111:11948–60 [Google Scholar]
  69. Neville S, Wang Y, Boguslavskiy A, Stolow A, Schuurman M. 69.  2016. Substituent effects on dynamics at conical intersections: allene and methyl allenes. J. Chem. Phys. 144:014305 [Google Scholar]
  70. Hudock HR, Levine BG, Thompson AL, Satzger H, Townsend D. 70.  et al. 2007. Ab initio molecular dynamics and time-resolved photoelectron spectroscopy of electronically excited uracil and thymine. J. Phys. Chem. A 111:8500–8 [Google Scholar]
  71. MacDonell RJ, Schalk O, Geng T, Thomas RD, Feifel R. 71.  et al. 2016. Excited state dynamics of acrylonitrile: substituent effects at conical intersections interrogated via time-resolved photoelectron spectroscopy and ab initio simulation. J. Chem. Phys. 145:114306 [Google Scholar]
  72. Nenov A, Cordes T, Herzog T, Zinth W, de Vivie-Riedle R. 72.  2010. Molecular driving forces for Z/E isomerization mediated by heteroatoms: the example hemithioindigo. J. Phys. Chem. A. 114:13016–30 [Google Scholar]
  73. Martínez TJ. 73.  2006. Insights for light-driven molecular devices from ab initio multiple spawning excited-state dynamics of organic and biological chromophores. Acc. Chem. Res. 39:119–26 [Google Scholar]
  74. Virshup AM, Levine BG, Martínez TJ. 74.  2014. Steric and electrostatic effects on photoisomerization dynamics using QM/MM ab initio multiple spawning. Theor. Chem. Acc. 133:1506 [Google Scholar]
  75. Hockett P, Ripani E, Rytwinski A, Stolow A. 75.  2013. Probing ultrafast dynamics with time-resolved multi-dimensional coincidence imaging: butadiene. J. Mod. Opt. 60:1409–25 [Google Scholar]
  76. Blanchet V, Zgierski MZ, Seideman T, Stolow A. 76.  1999. Discerning vibronic molecular dynamics using time-resolved photoelectron spectroscopy. Nature 401:52–54 [Google Scholar]
  77. Schalk O, Boguslavskiy A, Stolow A. 77.  2010. Substituent effects on dynamics at conical intersections: cyclopentadienes. J. Phys. Chem. A 114:4058–64 [Google Scholar]
  78. Schalk O, Boguslavskiy A, Schuurman M, Brogaard R, Unterreiner A. 78.  et al. 2013. Substituent effects on dynamics at conical intersections: cycloheptatrienes. J. Phys. Chem. A 117:10239–47 [Google Scholar]
  79. McNaught AD, Wilkinson A. 79.  1997. IUPAC Compendium of Chemical Terminology Oxford: Blackwell Sci, 2nd ed..
  80. Deb S, Weber P. 80.  2011. The ultrafast pathway of photon-induced electrocyclic ring-opening reactions: the case of 1,3-cyclohexadiene. Annu. Rev. Phys. Chem. 62:19–39 [Google Scholar]
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